CN102469775B

CN102469775B - A process for preparing an aqueous suspension of an organic pesticide compound

Info

Publication number: CN102469775B
Application number: CN201080031803.3A
Authority: CN
Inventors: C·W·芬奇
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2009-07-14
Filing date: 2010-07-13
Publication date: 2014-02-26
Anticipated expiration: 2030-07-13
Also published as: IL217241A0; UA103689C2; MX2012000787A; JP5941406B2; IL217241B; CR20120015A; EP2453739B2; WO2011006896A3; AU2010272571A1; CA2766711C; AU2010272571B2; DK2453739T3; BR112012000585B1; US20120128750A1; PE20121206A1; ES2439284T5; EA020180B1; EA201200117A1; CN102469775A; JP2012532911A

Abstract

The present invention relates to a process for preparing an aqueous suspension of an organic pesticide compound, which has a solubility in water of not more than 2 g/l at 20 DEG C and a melting point of not more than 110 DEG C and which is capable of forming at least one crystalline modification, wherein the organic pesticide compound is present in the form of essentially crystalline particles, which process comprises: a) providing an aqueous emulsion of the organic pesticide compound, wherein the organic pesticide compound is present in the form droplets of an amorphous form of the organic pesticide compound, and b) addition of an aqueous suspension of said organic pesticide compound, wherein the organic pesticide compound is present in the form of essentially crystalline particles, wherein the addition in step b) is performed at a temperature below the melting temperature of the crystalline form of the organic pesticide compound.

Description

The method of preparing the aqueous suspension of organic agricultural chemical compound

The present invention relates to a kind of method of preparing the aqueous suspension of organic agricultural chemical compound, water-soluble the be no more than 2g/l of this compound at 20 ℃ and fusing point are no more than 110 ℃ and can form at least one crystal formation, and wherein this organic agricultural chemicals compound exists with the particle form of basic crystallization.

There is low aqueous solubility, the organic agricultural chemicals compound of the water-soluble 2g/l of being no more than under 20 ℃/1013 millibars is mixed with aqueous suspension concentrate conventionally, also referred to as SC (or be called FS preparaton the seed treatment preparaton in the situation that, or be called simply FS).In SC and equally in FS preparaton, agricultural chemicals exists with fine dispersion particle form, these particles are suspended in aqueous liquid phase, beyond this liquid phase dewaters, conventionally contain at least one surfactant to stablize pesticide granules and can contain other additive preparations as rheology modifiers, biocide, dyestuff, defoamer (antifoaming agent) and antifreezing agent.SC is dilute with water the easy processing mode at large Tanaka's applying pesticides is therefore provided easily conventionally.Therefore in addition, SC and FS only contain on a small quantity or conventionally even containing organic volatile and because environment reason is preferred.

Although the above-mentioned advantage relevant with FS to using SC, but there is the known problem of many those of skill in the art, these problems sometimes due to long term storage or at elevated temperatures the sedimentation in storage process, sedimented particle resistance to suspension again and form crystalline material while storing and run into by SC and FS.Therefore, preparaton may be difficult to process and biopotency may be inconsistent.

When low melting point organic agricultural chemicals is mixed with to SC, may in preparation process, meet difficulty.SC and FS are conventionally by being suspended in one or more organic agricultural chemicals compounds in the water that contains suitable surfactant and optional other additive preparations and prepared by pesticide granules to the desired particle size of comminuted suspension.Yet this organic agricultural chemicals compound of the method major requirement is solid-state, is preferably crystalline state, because this organic agricultural chemicals may stop up milling apparatus.For low melting point agricultural chemicals, be conventionally difficult to prepare solid material, especially crystalline material.In addition, this agricultural chemicals may the melting in crushing process owing to pulverizing the mechanical energy introduce, thereby causes the obstruction of milling apparatus.

Repeatedly someone advises preparing by melt emulsification method the aqueous suspension concentrate of low melting point, water-insoluble organic compound.In this melt emulsification method, by mixture being applied to high shear and the organic compound of melting being emulsified in water, chilling then.Melt emulsification obtains aqueous suspension or aqueous emulsion conventionally, and wherein the active ingredient particle of suspension/emulsification exists to cross the drop form of sloppy heat body.

EP-A 249075 discloses a kind of method of preparing the aqueous suspension concentrate preparaton of low melting point agricultural chemicals pendimethalin (pendimethalin), the method is included in emulsification melting pendimethalin in the aqueous solution that contains surfactant and defoamer, and this emulsion is cooling to solidify the pendimethalin drop suspension that also grinding so obtains to the desired particle size of pendimethalin particle.

EP-A 145 879 discloses a kind of method of preparing the aqueous suspension of agricultural chemical compound, wherein the agricultural chemical compound of melting is metered in the cold jet of the aqueous solution of additive preparation.Yet the method is limited to the agricultural chemical compound that fusing point is significantly higher than 70 ℃.

EP-A 1060667 discloses a kind of method of preparing the aqueous suspension concentrate of water-insoluble crystallization active substance, wherein the material stream of melting active substance is merged with aqueous solvent material stream under shear conditions in mixing chamber, thereby this melting active substance of emulsification, is wherein chosen in time of staying in mixing chamber so that this emulsion is cooled to below the fusing point of active substance and active material particle solidifies before leaving mixing chamber.Yet the method is limited to the agricultural chemical compound of rapid crystallization when cooling.

Although these methods mainly allow to prepare the aqueous suspension concentrate of water-insoluble agricultural chemical compound, they have several limitations or shortcoming.For example, gained suspending concentrate may have limited stability, especially when this agricultural chemical compound has low melting point and/or show slow crystalline rate when cooling.This is because this agricultural chemical compound particle may not controlled particle growth occur because of " Ostwald ripening ", because the residual solvability of this agricultural chemicals in aqueous suspension medium may be enough to allow crystallization process as the phase change of the crystallization of amorphous materials or allotropy form (if this agricultural chemicals can form polymorphic words).These problems become obvious while storing at the temperature that raising and/or that change by suspending concentrate.

Pyraclostrobin (Pyraclostrobin) (IUPAC:{2-[1-(4-chlorphenyl) pyrazole-3-yl oxygen ylmethyl] phenyl } (methoxyl group) methyl carbamate; CAS 175013-18-0) be low melting point fungicide compound, its fusing point is lower than 68 ℃.The actual water fast of pyraclostrobin (solvability < 2mg/l at 20 ℃) is (for example, referring to Herms, S., Seehaus, K., Koehle, H. and Conrath, U. (2002) Pyraclostrobin-" More than just a Fungicide " Phytomedizin 32:17; C.D.S.Tomlin (editor), " The Pesticide Manual ", the 14th edition, BCPC Publications Hampshire 2006).Known pyraclostrobin exists with four kinds of different enantiotropy crystalline form (crystal formation) I-IV, and form IV is crystalline form (seeing WO 2006/136357) the most stable on thermodynamics.Although the aqueous suspension concentrate of pyraclostrobin is described in the art, they are especially because the low melting point of pyraclostrobin is difficult to prepare by conventional method.In addition, the preparation of crystallization pyraclostrobin current be therefore that effort is time-consuming and improved the cost of the aqueous suspension concentrate of preparing pyraclostrobin.

Therefore, the object of this invention is to provide a kind of method of preparing stable aqueous formulation with aqueous suspension concentrate form, this preparaton comprises at least one not to be had water-soluble or only has limited water-soluble and have an organic agricultural chemicals compound of low melting point.Shortcoming and the method that the method should overcome prior art should allow to prepare the stable suspersion concentrate that has low melting point and can form the agricultural chemical compound of crystalline material.The method should be particularly suitable for preparing the stable aqueous suspending concentrate of the crystalline form I V that contains pyraclostrobin, especially pyraclostrobin.

Have now found that these and other objects are realized by a kind of method of preparing the aqueous suspension of organic agricultural chemical compound, water-soluble the be no more than 2g/l of this compound at 20 ℃ and fusing point are no more than 110 ℃ and can form at least one crystal formation, wherein this organic agricultural chemicals compound exists with the particle form of basic crystallization, and described method comprises the following steps a) and b):

A) provide the aqueous emulsion of this organic agricultural chemicals compound, wherein this organic agricultural chemicals compound exists with the drop form of the amorphous form of this organic agricultural chemicals compound, and

B) add the aqueous suspension of described organic agricultural chemicals compound, wherein this organic agricultural chemicals compound exists with the particle form of basic crystallization, at the temperature of wherein feeding in raw material below the melt temperature of the crystalline form of this organic agricultural chemicals compound, carries out.

The present invention is based on following surprising discovery: at the temperature below the fusing point of low melting point and microsolubility or insoluble organic agricultural chemicals compound, to the aqueous suspension that adds the basic crystalline particle that contains on a small quantity described agricultural chemical compound in the aqueous emulsion of described agricultural chemical compound, brought out the quick and complete crystallization of the amorphous drop that is contained in this agricultural chemical compound in this aqueous emulsion, and do not cause the formation of thick material, thereby obtain the stable aqueous suspensions of this organic agricultural chemicals compound, wherein this organic agricultural chemicals compound exists with the particle form of basic crystallization.

Therefore, the present invention relates to a kind of method of preparing the aqueous suspension of organic agricultural chemical compound, this compound has limited water-soluble, the i.e. water-soluble 2g/l of being no more than at 20 ℃ and have and be conventionally no more than the low melting point of 110 ℃ and can form at least one crystalline form, wherein this organic agricultural chemicals compound exists with the particle form of basic crystallization, and described method comprises:

B) add the aqueous suspension of described organic agricultural chemicals compound, wherein this organic agricultural chemicals compound exists with the particle form of basic crystallization,

Step b wherein) at the temperature of feeding in raw material below the melt temperature of the crystalline form of this organic agricultural chemicals compound in, carry out.

The method is particularly suitable for the stable aqueous suspensions that preparation has limited water-soluble and low melting point and can form the organic agricultural chemicals compound of at least one stable crystalline forms.

In addition, the inventive method has several benefits.Particularly, the inventive method does not require prepared a large amount of solid crystal materials of this agricultural chemical compound and therefore not too consuming time and avoided the processing of solid crystal material before preparation, and this processing may be a problem especially when this agricultural chemicals has low melting point.In addition, the inventive method does not require the crushing technology of preparing common desired effort in aqueous suspension concentrate.

Step b in method required for protection) these stable suspensions that obtain in can directly be used as the aqueous suspension concentrate preparaton of described agricultural chemical compound or can be used as other preparatons; especially the basic material of aqueous suspension concentrate preparaton, described preparaton contains and has low melting point and limited water miscible described low melting point agricultural chemical compound and one or more and at 20 ℃, have the combination of limited water miscible other agricultural chemical compounds that are conventionally no more than 2g/l.

Therefore, the invention still further relates to a kind of method of preparing aqueous pesticide preparaton with the aqueous suspension concentrate form that contains at least one organic agricultural chemicals compound, water-soluble the be no more than 2g/l of this compound at 20 ℃ and fusing point are no more than 110 ℃ and can form at least one crystal formation, the method comprises the aqueous suspension of preparing this organic agricultural chemicals compound by methods described herein, and wherein this organic agricultural chemicals compound exists with the particle form of basic crystallization.

" limited water-soluble " refers to for the present invention this agricultural chemical compound water fast or the water-soluble 3g/l of being no more than under 20 ℃ (1013 millibars) or is no more than 2g/l, particularly be no more than 1g/l, preferably be no more than 0.5g/l, especially be no more than 0.1g/l, 0-2g/l for example, particularly 0.01mg/l-1g/l or 0.02mg/l-0.5g/l, especially 0.05mg/l-0.1g/l.Solvability is measured conventionally at 20 ℃ in deionized water.

" low melting point " refers to that the fusing point of this agricultural chemical compound is no more than 110 ℃ for the present invention, is particularly no more than 95 ℃, is preferably no more than 80 ℃, is especially no more than 70 ℃, for example 40-100 ℃, particularly 45-90 ℃, preferably 50-80 ℃, especially 55-70 ℃.

" can form at least one stable crystalline forms " and refer to for the present invention crystalline material and this crystalline material that this agricultural chemical compound can be formed in 25 ℃ of above meltings and preferably there are at least 40 ℃, particularly at least 45 ℃, more preferably at least 50 ℃, the fusing point of at least 55 ℃ especially.

" basic crystallization " refers to that these agricultural chemical compound at least 90 % by weight that are present in aqueous suspension are crystalline state and are present in this agricultural chemical compound in aqueous suspension that to be less than 10 % by weight be not crystallization, are unbodied for the present invention.Degree of crystallinity can be measured by powder x-ray diffraction (powder X-ray RD), the optical microscopy (due to the birefringence of crystalline phase) of this agricultural chemical compound simply, in most of the cases also by dsc analysis (DSC=differential scanning calorimetry), measured, and in some cases by IR spectrographic determination.

" amorphous form " refers to that this agricultural chemical compound of being present in aqueous emulsion is substantially for crystallization for the present invention, and its total amount based on this agricultural chemical compound contains the crystalline material that is less than 10 % by weight or untraceable amount.Amorphous form comprises liquid form, i.e. melt and excessively sloppy heat body and solid amorphous form.

The inventive method be applicable to preparation have as defined above limited water-soluble and as above to low melting point and can form the stable aqueous suspensions of any organic agricultural chemicals compound of at least one stable crystalline forms.The example of such organic agricultural chemicals compound include but not limited to following table to compound:

Agricultural chemical compound	Fusing point [℃]	Water-soluble ¹⁾[mg/l]
			Aldrin (aldrin)	49-60	＜＜1
Alachlor (alachlor)	39.5-41.5	242
			Triazotion (azinphos-ethyl)	74	33
Benfluralin (benfluralin)	65-66.5	＜1
			Bensultap (bensultap)	82-83	0.7
Citrazon (benzoximate)	73	30
			Bifenthrin (bifenthrin)	51-66	0.1
Binapacryl (binapacryl)	66-67	＜＜0.1
			Bromophos (bromophos)	53-54	40
Fenisobromolate (bromopropylate)	77	＜5
			Amex820 (butralin)	60-61	1
Chlorphoxim (chlorphoxim)	66.5	2
			Chlopyrifos (chlorpyriphos)	42-43.5	2

Agricultural chemical compound	Fusing point [℃]	Water-soluble ¹⁾[mg/l]
			Fluchloralin (fluchloralin)	42-43.5	＜1
Fluroxypyr (fluroxypyr)	56-57	0.9
			Imines bacterium (kresoxim-methyl)	97	2
Lorox (linuron)	93-94	75
			Metazachlor (metazachlor)	80	450
Encircle penta azoles bacterium (metconazol)	100-104.2	1400
			Afesin (monolinuron)	92-94	735
Proproanmide (napropamide)	75	73
			Isopropyl disappear (nitrothal-isopropyl)	65	0.4
Pendimethalin	54-58	0.3
			Phosmet (phosmet)	72.5	25
ZEN 90160 (picoxystrobin)	53-75	3.1
			Aphox (pirimicarb)	90.5	2700
Fluorine pyrrole acyl grass amine (picolinafen)	107-108	＜0.1
			Pyraclostrobin	55-64 ²⁾	1.9
Tefluthrin (tefluthrin)	44.6	0.02
			Oxime bacterium ester (trifloxystrobin)	80	450

1) water-soluble in deionized water at 20 ℃

2) depend on polymorphic

The inventive method is particularly suitable for preparing the stable aqueous suspensions of pyraclostrobin.The inventive method is especially applicable to preparing the stable aqueous suspensions of the crystalline form I V of pyraclostrobin, and in the aqueous suspension so obtaining, contained pyraclostrobin exists as the crystalline form I V (also claiming form IV) of pyraclostrobin substantially.Therefore, particularly preferred embodiment of the present invention relates to following method: wherein in step emulsion a) contained agricultural chemical compound be pyraclostrobin and wherein at step b) in the crystalline pesticide compound that exists in the aqueous suspension that adds be basic crystallization pyraclostrobin, especially pyraclostrobin exist with its crystalline form I V substantially.

For the present invention, " the crystalline form I V (or form IV) with pyraclostrobin exists substantially " refers to that the pyraclostrobin at least 90% being present in aqueous suspension concentrate exists with its crystalline form I V.

The crystalline form I V of pyraclostrobin is described in WO 2006/136357 for the first time, and this application all as a reference.Crystalline form I V can be identified by its characteristic X-ray diffraction pattern, in its X-ray powder diffraction figure at 25 ℃, demonstrates at least 3 in following reflection, especially at least 4, preferably whole:

The crystallization pyraclostrobin of form IV has the fusing point of 62-64 ℃ conventionally.Melting heat, melting form IV institute energy requirement is about 72-80J/g.Here fusing point shown in and melting heat refer to the value of being measured by differential calorimetry (differential scanning calorimetry: DSC, crucible material aluminium, rate of heat addition 5K/min).

The monocrystalline research of form IV shows that basic crystal structure is monoclinic system and has space group P2 (1)/c.The characteristic of the crystal structure of crystalline form I V (form IV) is summarized in table 1:

Table 1: the crystallography data of form IV

Parameter	Form IV
		Classification	Monoclinic system
Space group	P2(1)/c
		a	998.5(3)pm
b	4780.4(10)pm
		c	788.6(2)pm
α	90°
		β	105.357(6)°
γ	90°
		Volume	3.6301(16)nm ³
Z	8
		Density (calculated value)	1.419g/cm ³
R1，wR2	0.0651，0.1574

A, b, the c=structure cell length of side

α, beta, gamma=structure cell angle

Molecular number in Z=structure cell

The preparation of the crystalline form I V of crystallization pyraclostrobin, especially pyraclostrobin is also described in WO 2006/136357, and this application all as a reference.

According to the inventive method, the aqueous emulsion of this organic agricultural chemicals compound is provided, wherein this organic agricultural chemicals compound exists with the drop form of the amorphous form of described organic agricultural chemicals compound.Amorphously refer to that this agricultural chemical compound does not exist with its crystalline state substantially, this means that in this amorphous agricultural chemical compound, crystalline material amount is less than 10 % by weight.Amorphous agricultural chemical compound for example can or be crossed sloppy heat body or amorphous solid exists with melt.Average droplet size, the volume mean diameter of drop is preferably 0.5-10 μ m, 1-5 μ m especially, this is by Dynamic Light Scattering Determination.

Average grain diameter mentioned in this article is volume average particle size d (0.5) or d (v, 0.5), the diameter of mean value and 50 volume % particles shown in the diameter that particle of 50 volume % has exceeds lower than shown in mean value.Therefore, average grain diameter is also referred to as " volume median diameter ".This average grain diameter can be measured by dynamic light scattering (conventionally the diluted suspension that contains 0.01-1 % by weight active component being carried out).Those of skill in the art know these methods, and they are for example described in H.Wiese (D.Distler, editor), Aqueous Polymer Dispersions (

polymerdispersionen), Wiley-VCH 1999, the 4.2.1 chapters, the 40th page and each page and the document wherein quoted subsequently; H.Auweter, D.Horn, J.Colloid Interf.Sci.105 (1985), the 399th page; D.Lilge, D.Horn, Colloid Polym.Sci.269 (1991), the 704th page and H.Wiese, D.Horn, J.Chem.Phys.94 (1991), in the 6429th page.

The gross weight of the amount of agricultural chemical compound in emulsion based on this emulsion is generally 5-60 % by weight, preferably 10-50 % by weight, especially 20-45 % by weight.

Except agricultural chemical compound, this emulsion is included as the water of the dispersion medium of this agricultural chemical compound drop.Beyond dewatering, this water can contain the surfactant that one or more are adapted at stable droplet in water conventionally.

Suitable surfactant comprises anion surfactant, non-ionic surface active agent and cationic surfactant or its combination.Surfactant comprises also referred to as the non-polymer surfactant of emulsifier and also can be called the polymeric surfactant of protective colloid.Contrary with polymeric surfactant, emulsifier conventionally has and is no more than 1000 daltonian number-average molecular weight M _n, and polymeric surfactant conventionally has and is greater than 1000 daltonian number-average molecular weight M _n.The character of surfactant is particular importance not, and for example they can be selected from any known dispersant and wetting agent.Dispersant is for example by ionic and/or hydrophobic interaction, to be mainly bonded to active ingredient particle/drop those surfactants surperficial and stable particle in liquid phase.Wetting agent is the surfactant that mainly reduces liquid phase and dispersion or be emulsifiable in the interfacial tension between the surface of solid particle of active component in water (being agricultural chemical compound) here, helps thus particle stabilized in water.Wetting agent can be selected by the physical measurement of contact angle.The contact angle that specially suitable wetting agent has is less than 90 °, is especially less than 60 ° (according to DIN 53914, by Wilhelmy method or according to the supplementary Washburn method of the powder of this agricultural chemical compound of use, under 24 ℃/1013 millibars, 1M wetting agent solution being measured).

This aqueous emulsion conventionally based on this emulsion gross weight with 0.1-20 % by weight, preferred 0.5-15 % by weight, especially the amount of 1-10 % by weight contains at least one surfactant.The weight ratio of agricultural chemicals and surfactant is generally 2: 1-50: 1, particularly 3: 1-20: 1.

Suitable surfactant is well-known to those of skill in the art as its preparation method; They also can be commercial, for example every kind of situation with following trade name.

The surfactant being preferably contained in this aqueous emulsion comprises at least one anion surfactant.In very preferably embodiment of the present invention, this surfactant additionally comprises at least one non-ionic surface active agent.If the combination that this aqueous emulsion contains at least one anion surfactant and at least one non-ionic surface active agent, the weight ratio of anion surfactant and non-ionic surface active agent is preferably 1: 5-5: 1, especially 1: 3-3: 1.Yet this emulsion can also only comprise one or more non-ionic surface active agents.The surfactant being preferably contained in this aqueous emulsion comprises at least one polymeric surfactant.In very preferably embodiment of the present invention, this surfactant additionally comprises at least one non-polymer surfactant.If the combination that this aqueous emulsion contains at least one polymeric surfactant and at least one non-polymer surfactant, the weight ratio of polymeric surfactant and non-polymer surfactant is preferably 1: 5-5: 1, especially 1: 3-3: 1.Yet this emulsion can also only comprise one or more non-ionic surface active agents.

Anion surfactant especially comprises sodium, potassium, calcium or the ammonium salt of following compound :-there is SO ₃ ^-or PO ₃ ^2-the non-polymeric anion surfactant of group, for example

C.1 C ₆-C ₂₂alkylsulfonate is as lauryl sulfonate, isotridecyl sulfonate;

C.2 C ₆-C ₂₂alkyl sulfate is as lauryl sulfate, isotridecyl sulphate, cetyl sulphate, stearin-based sulfate;

C.3 aryl-and C ₁-C ₁₆alkylaryl sulfonate is as naphthyl sulfonate, single-, two-and three-C ₁-C ₁₆alkyl naphthyl sulfonate is as dibutyl naphthyl sulfonate, dodecyl diphenyl ether sulfonate, single-, two-and three-C ₁-C ₁₆alkyl benzene sulfonate is as cumyl sulfonate, octyl group benzene sulfonate, nonylbenzene sulfonates, dodecyl benzene sulfonate and tridecyl benzene sulfonate;

C.4 C ₆-C ₂₂fatty acid and C ₆-C ₂₂the sulphate of fatty acid ester and sulfonate;

C.5 ethoxylation C ₆-C ₂₂the sulphate of alkanol is as the sulphate of (gathering) ethoxylation laruyl alcohol;

C.6 (gather) ethoxylation C ₄-C ₁₆the sulphate of alkyl phenol and (gathering) ethoxylation two-or the sulphate of triphenyl vinyl phenol;

C.7 the list of phosphorous acid-and diester, comprises the mixture of itself and its three esters and salt, especially with C ₈-C ₂₂alkanol, ethoxylation C ₈-C ₂₂alkanol, C ₄-C ₂₂alkyl phenol, (gathering) ethoxylation C ₄-C ₂₂alkyl phenol, (gathering) ethoxylation two-or the ester of triphenyl vinyl phenol; With

C.8 two-C of sulfosuccinic acid ₄-C ₁₆arrcostab is as dioctylsulfosuccinat;

-there is SO ₃ ^-or PO ₃ ^2-the polymer anion surfactant of group, for example

C.9 aryl sulfonic acid is as the condensation product of naphthalene sulfonic acids or phenolsulfonic acid and formaldehyde and optional urea;

-there is the non-polymer anion surfactant of at least one carboxylate groups, for example

C.10 fatty acid is as stearate, and

C.11 N-C ₆-C ₂₂acylamino acid, as N-C ₆-C ₂₂acyl glutamate, N-C ₆-C ₂₂acylglycine salt and N-C ₆-C ₂₂acyl sarcosinates;

-there is the polymer anion surfactant of carboxylate groups, for example

C.12 contain the gather-C being grafted on polymer backbone ₂-C ₄anionic grafting or the comb copolymer of alkylene oxide structure part, especially polyoxyethylene structure division PEO and the carboxylate groups being connected with polymer backbone;

C.13 with polymerized form, contain (i) C ₃-C ₅monoethylenically unsaturated carboxylic acid monomer and (ii) the water-soluble anionic copolymer that is no more than the hydrophobic monomer of 60g/l under 20 ℃ and 1013 millibars.

In anion surfactant, those that preferably c.3, c.6, c.8, c.8, c.9, c.12 and c.13 organize and composition thereof.

C.3 organizing in surfactant, preferred list-or two-C ₄-C ₈alkyl naphthalene sulfonic acid and list-or two-C ₄-C ₁₆alkyl benzene sulphonate and ammonium salt thereof, alkali metal salt is as sodium or sylvite and alkali salt, especially calcium salt.Specially suitable example is Morwet eFW (Akzo Nobel) etc.

C.6 organizing in surfactant, preferably (gather) ethoxylation two-or triphenyl vinyl phenol, especially there is 5-50, especially those ammonium sulfate, sulfuric acid alkali metal salt and sulfuric acid alkali salt of 10-50 or 15-50 ethylene oxide repetitive.(gathering) ethoxylation two-or the special suitable example of the sulphate of triphenyl vinyl phenol be the Soprophor of Rhodia

4D384 etc.

C.7 organizing in surfactant, preferably (gather) ethoxylation two-or triphenyl vinyl phenol, especially has 5-50, especially those ammonium phosphate salt and phosphoric acid alkali metal salt of individual or 15-50 the ethylene oxide repetitive of 10-50.

C.8 organizing in surfactant, preferably sulfosuccinic acid two (C ₆-C ₁₂alkyl) ammonium salt of ester and alkali metal salt, C ₆-C ₁₂alkyl is straight chain or the branched-alkyl with 6-12 carbon atom, for example n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, 2-hexyl, 2-heptyl, 2-octyl group, 2-nonyl and 2-ethylhexyl.Preferably use dioctylsulfosuccinat alkali metal salt, wherein octyl group structure division can be linearity or branching and wherein alkali metal be selected from sodium and potassium.Specially suitable example is Aerosol oTB (Cytec) etc.

C.9 organizing in surfactant, aryl sulfonic acid can be not for example to be substituted or by one or more, for example 1,2,3 or 4 C ₁-C ₂₀phenolsulfonic acid or naphthalene sulfonic acids that alkyl replaces.In preferred embodiments, c.9 surfactant is alkali metal salt or the alkali salt of the product (condensation product) of naphthalene sulfonic acids and formaldehyde; Specially suitable example is Morwet

d425 (Akzo Nobel).In another preferred embodiment, c.9 surfactant is alkali metal salt or the alkali salt of the product (condensation product) of phenolsulfonic acid, formaldehyde and urea; Specially suitable example is Wettol

d1 (BASF SE).

C.12 preferred grafting or the comb copolymer of group preferably contain with polymerized form:

(i) at least one C ₃-C ₅monoethylenically unsaturated carboxylic acid monomer, as acrylic acid, methacrylic acid or maleic acid,

(ii) at least one has be connected with polymerisable ethylenical unsaturated double bonds via ester bond or ehter bond oligomeric-or poly--C ₂-C ₄oxyalkylene group, especially oligomeric-or the monomer of polyoxyethylene group, particularly oligomeric-or poly--C ₂-C ₄the ester of oxyalkylene, especially oligomeric-or polyoxyethylene and C ₃-C ₅monoethylenically unsaturated carboxylic acid monomer is as the ester of acrylic or methacrylic acid, or oligomeric-or poly--C ₂-C ₄oxyalkylene list-C ₁-C ₄the ester of alkyl ether, especially oligomeric-or polyoxyethylene list-C ₁-C ₄alkyl ether and C ₃-C ₅monoethylenically unsaturated carboxylic acid monomer is as the ester of acrylic or methacrylic acid,

(iii) hydrophobic monomer of the optional water-soluble 60g/l of being no more than having under 20 ℃ and 1013 millibars, for example C ₃-C ₅the C of monoethylenically unsaturated carboxylic acid monomer ₁-C ₁₀arrcostab, particularly acrylic or methacrylic acid C ₁-C ₁₀arrcostab (acrylic acid C ₁-C ₁₀arrcostab and methacrylic acid C ₁-C ₁₀arrcostab), for example methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, vi-ny l aromatic monomers is as styrene and C ₂-C ₁₂monoolefine is as ethene, propylene, 1-butylene, isobutene, hexene, 2-ethyl hexene, diisobutylene (Isobutylene Dimers mixture), tripropylene, polypropylene tetramer, triisobutylene etc.In surfactant preferred embodiment c.12, the ester that grafting or comb-shaped polymer contain methacrylic acid, methyl methacrylate and polyoxyethylene monomethyl ether and methacrylic acid with polymerized form or consist of it, can Tersperse as what be 1000934-04-1 at No. CAS 2500 commercial copolymers and be 119724-54-8 No. CAS can Atlox

the same in 4913 commercial copolymers.

C.12 the grafting of group or the weight average molecular weight of comb copolymer are preferably 5000-800000g/mol, particularly 7500-600000g/mol, especially 10000-400000g/mol.C.12 the grafting of group or comb copolymer are preferably not crosslinked.

C.13 the preferred polymers surfactant of group is to contain (i) at least one C with polymerized form ₃-C ₅monoethylenically unsaturated carboxylic acid monomer and (ii) at least one those of hydrophobic monomer as defined above.Suitable C ₃-C ₅monoethylenically unsaturated carboxylic acid monomer and suitable hydrophobic monomer are those that mention in group c.12.Preferred C ₃-C ₅monoethylenically unsaturated carboxylic acid monomer comprises acrylic acid, methacrylic acid and maleic acid.Preferred hydrophobic monomer is selected from vi-ny l aromatic monomers as styrene monomer and C ₂-C ₁₂monoolefine.C.13, preferred polymers surfactant contains (i) at least one C with polymerized form ₃-C ₅monoethylenically unsaturated carboxylic acid monomer, especially acrylic or methacrylic are sour, and (ii) at least one is selected from styrene monomer and C ₂-C ₁₂the hydrophobic monomer of monoolefine.The weight ratio of acid monomers and hydrophobic monomer is preferably 10: 1-1: 3; Preferably 5: 1-1: 2.Surfactant special suitable example is c.13 Atlox

metasperse 500L (Uniqema) etc.

Non-ionic surface active agent especially comprises:

C.14 polyethylene glycol-C ₁-C ₂₂alkyl ether, polyethylene/polypropylene glycol-C ₁-C ₂₂alkyl ether, especially linearity or branching C ₈-C ₂₀the polyethoxylate of alkanol and polyethoxylate-co-propoxylate, more preferably polyethoxylated C ₈-C ₂₂fatty alcohol and polyethoxylated C ₈-C ₂₂oxo alcohol, as polyethoxylated laruyl alcohol, the different tridecanol of polyethoxylated, polyethoxylated cetanol, polyethoxylated stearyl alcohol, polyethoxylate-co-propoxylate of laruyl alcohol, polyethoxylate-co-propoxylate of cetanol, polyethoxylate-co-propoxylate of different tridecanol, stearyl alcohol polyethoxylate-co-propoxylate, and their ester, as acetic acid esters;

C.15 polyethylene glycol aryl ether and polyethylene/polypropylene glycol aryl ether, especially single-or two-C ₁-C ₁₆the polyethoxylate of alkyl phenol and polyethoxylate-co-propoxylate, as the polyethoxylate of nonyl phenol, decyl phenol, isodecyl phenol, dodecylphenol or isotridecyl phenol and polyethoxylate-co-propoxylate, and their ester, as acetic acid esters;

C.16 C ₆-C ₂₂alkyl glucoside and C ₆-C ₂₂alkyl polyglucoside;

C.17 polyalcohol and C ₆-C ₂₂the list of part ester, the especially glycerine of alkanoic acid-and the list of diester and anhydro sorbitol-, two-and three esters, as glyceryl monostearate, Arlacel-80, Arlacel-65;

C.18 C ₆-C ₂₂the polyethoxylate of alkyl glucoside and C ₆-C ₂₂the polyethoxylate of alkyl polyglucoside;

C.19 C ₆-C ₂₂the polyethoxylate of fatty amine and polyethoxylate-co-propoxylate;

C.20 C ₆-C ₂₂the polyethoxylate of fatty acid and polyethoxylate-co-propoxylate and hydroxyl C ₆-C ₂₂the polyethoxylate of fatty acid and polyethoxylate-co-propoxylate;

C.21 polyalcohol and C ₆-C ₂₂the polyethoxylate of the part ester of alkanoic acid, especially the list of glycerine-and the polyethoxylate of diester and list of anhydro sorbitol-, two-and the polyethoxylate of three esters, as the polyethoxylate of the polyethoxylate of the polyethoxylate of the polyethoxylate of glyceryl monostearate, Arlacel-80, Arlacel-60 and Arlacel-65;

C.22 the polyethoxylate of vegetable oil or animal tallow is as corn oil ethoxylate, castor oil ethoxylate, fatty oil ethoxylate;

C.23 the polyethoxylate of fatty amine, fatty acid amide or fatty diglycollic amide;

C.24 single-, two-and polyethoxylate and the polyethoxylate-co-propoxylate of triphenyl vinyl phenol, and their ester, as acetic acid esters; And

C.25 comprise at least one poly-(oxygen ethene) structure division PEO and be derived from C with at least one ₃-C ₁₀non-ionic block copolymer, the especially polyox-yethylene-polyoxypropylene block copolymer of the polyether structure part PAO of oxyalkylene and/or styrene oxide;

C.26 the non-ionic graft copolymers that contains the polyoxyethylene structure division PEO grafting on nonionic, hydrophilic polymers skeleton.

Term polyethylene glycol, polyethoxylate and polyethoxylated refer to the polyether group that is derived from ethylene oxide.Equally, term polyethoxylate-co-propoxylate refers to the polyether group of the mixture that is derived from ethylene oxide and propylene oxide.Therefore, polyethoxylate has formula [CH ₂cH ₂o] repetitive, and polyethoxylate-co-propoxylate has formula [CH ₂cH ₂o] and [CH (CH ₃) CH ₂o] repetitive.C.14, c.15 and c.18-c.24 surfactant may belong to non-polymer group of surfactants or polymeric surfactant group, and this depends on the number of oxyalkylene repeat units.In the surfactant of these groups, the number of such repetitive is generally 2-200, particularly 3-100, especially 3-50.C.25 and c.26 c.17 and c.18 the surfactant of group belongs to non-polymer surfactant, and the surfactant of group is generally polymeric surfactant.

In non-ionic surface active agent, those that preferably c.14, c.15, c.24, c.25 and c.26 organize and composition thereof.

C.14 organizing in surfactant preferred linear C ₈-C ₂₂the polyethoxylate of alkanol and poly-(ethoxylate-co-propoxylate).Same preferably C ₁-C ₁₀alkanol, particularly preferably poly-(ethoxylate-co-propoxylate) of butanols.Surfactant c.14 in, preferred number average molecular weight M _nbe no more than 5000 daltonian those.

C.15 organizing in surfactant, preferred list-or C ₈-C ₂₂the polyethoxylate of alkanol and poly-(ethoxylate-co-propoxylate).Same preferably C ₁-C ₁₀alkanol, particularly preferably poly-(ethoxylate-co-propoxylate) of butanols.Surfactant c.15 in, preferred number average molecular weight M _nbe no more than 5000 daltonian those.C particularly preferably ₁-C ₁₀poly-(ethoxylate-co-propoxylate) of alkanol, its number-average molecular weight M _nfor 500-5000 dalton.Specially suitable example comprises Atlox

g 5000 (Akzo Nobel), Tergitol

xD etc.

C.24 organizing in surfactant, phenoxy group is with 1,2 or 3 cinnamenyl structure part and polyoxyethylene structure division PEO or poly-(ethylene oxide-co-propylene oxide) structure division PEO/PPO.PEO structure division comprises 5-50 ethylene oxide group conventionally.Preferred surfactant c.24 can be by formula (C ₂h ₄o) _nc ₃₀h ₃₀o represents, integer and C that wherein n is 5-50 ₃₀h ₃₀o represents triphenyl vinyl phenol group.Specially suitable example is Soprophor

bSU (Rhodia).

C.25 the non-ionic block copolymer of organizing surfactant comprises at least one poly-(ethylene oxide) structure division PEO and is conventionally derived from one or more C with at least one ₃-C ₁₀the hydrophobicity polyether structure part PAO of oxyalkylene.PAO structure division comprises at least 3 conventionally, and preferably at least 5, especially 10-100 is derived from one or more C ₃-C ₁₀oxyalkylene is as propylene oxide, 1,2-butylene oxide, cis-or trans-2,3-butylene oxide or oxidation isobutene, 1,2-be oxidized amylene, 1, and 2-be oxidized hexene, 1, and 2-is oxidized decene and styrene oxide, wherein preferred C ₃-C ₄the repetitive of oxyalkylene (number all).Preferably PAO structure division comprises at least 50 % by weight, and more preferably at least 80 % by weight are derived from the repetitive of propylene oxide.PEO structure division comprises at least 3 conventionally, and preferably at least 5, more preferably at least 10 repetitives that are derived from ethylene oxide (number is all).The weight ratio of PEO structure division and PAO structure division (PEO: PAO) be generally 1: 10-10: 1, preferably 1: 10-2: 1, more preferably 2: 8-7: 3, especially 3: 7-6: 4.Preferred number average molecular weight M _nbe greater than 1200 dalton to 100000 dalton, preferably 2000-60000 dalton, more preferably daltonian those surfactants of 2500-50000 dalton, especially 3000-20000 c25).PEO structure division and PAO structure division account for non-ionic block copolymer surfactant c25 conventionally) at least 80 % by weight, preferably at least 90 % by weight, for example 90-99.5 % by weight.Suitable surfactant c25) be for example described in WO2006/002984, especially have wherein to those of formula P1-P5.

Described herein c.25 the non-ionic block copolymer surfactant of group for example can be commercial with following trade (brand) name: Pluronic

, as Pluronic

p 65, P84, and P 103, and P 105, and P 123, Pluronic PE 3500, PE 4300, and PE 4400, and PE 6200, and PE 6400, and PE 6800, and PE 9200, and PE 9400, and PE 10300, and PE 10400, PE 10500 and Pluronic

l 31, and L 43, and L 62, L 62LF, and L 64, and L 81, L 92 and L 121 (BASF SE); Pluraflo

, as Pluraflo

l860, L1030 and L 1060 (BASF SE); Tetronic

, as Tetronic

704,709,1104,1304,702,1102,1302,701,901,1101,1301 (BASF SE); Agrilan

aEC167 and Agrilan

aE C 178 (Akcros Chemicals); Antarox

b/848 (Rhodia); Berol 370 and Berol

374 (Akzo Nobel Surface Chemistry); Dowfax

50C15,63 N10,63 N30,64 N40 and 81 N10 (Dow Europe); Genapol

pF (Clariant); Monolan

, as Monolan

pB, Monolan

pC, Monolan

pK (Akcros Chemicals); Panox

pE (Pan Asian Chemical Corporation); Symperonic

, as Symperonic pE/L, Symperonic

pE/F, Symperonic

pE/P, Symperonic

pE/T (ICI surfactant); Tergitol xD, Tergitol

xH and Tergitol

xJ (Union Carbide); Triton

cF-32 (Union Carbide); Teric PE Series (Huntsman); And Witconol

, as Witconol

aPEB, Witconol

nS 500K (Akzo Nobel Surface Chemistry) etc.Preferred Pluronic wherein

and Pluraflo

block copolymer, specially suitable example is Pluronic

p105 and Pluraflo

1060 etc.Also particularly preferably number-average molecular weight MN is the list-C of the daltonian polyox-yethylene-polyoxypropylene block copolymer of 1000-10000 ₁-C ₁₀alkyl ether.Specially suitable example comprises Atlox

g 5000 (Uniqema), Tergitol

xD etc.

C.26 the preferred graft copolymer of group contains (i) C with polymerized form ₃-C ₅the methyl ester of monoethylenically unsaturated carboxylic acid monomer or hydroxyl-C ₂-C ₃arrcostab, as methyl acrylate, methyl methacrylate, hydroxyethyl acrylate and methacrylic acid hydroxyethyl ester, and the polyoxyethylene group (ii) being connected with polymer backbone via ester bond or ehter bond.In preferred embodiments, the polyethylene glycol oxide ester that surfactant skeleton c.26 contains methyl methacrylate and methacrylic acid with polymerized form.

In a preferred embodiment of the invention, this emulsion comprises at least one polymeric surfactant with at least one polyether group, especially has at least one polyether group, especially at least one poly--C ₂-C ₄the non-ionic polymer surfactant of alkylene ether group, or there is at least one polyether group, especially at least one poly--C ₂-C ₄the anionic polymer surfactant of alkylene ether group, or its mixture.There is at least one polyether group, especially at least one poly--C ₂-C ₄c.12 the preferred polymers surfactant of alkylene ether group be selected from, the polymeric surfactant and composition thereof of group c.24 and c.25.

In a preferred embodiment of the invention, this emulsion comprises at least one and has at least one polyether group, especially at least one poly--C ₂-C ₄especially c.24 or c.25 the non-ionic polymer surfactant of alkylene ether group, the non-ionic polymer surfactant of group.

In same preferred embodiment of the present invention, this emulsion comprises at least one anionic polymer surfactant with polyether lateral chain, in particular for the anionic polymer surfactant having with the polymer of the carbon skeleton of carboxylate groups and polyether lateral chain, especially c.12 the anionic polymer surfactant of organizing, particularly with polymerized form, contain methacrylic acid, the ester of methyl methacrylate and polyethylene glycol oxide monomethyl ether and methacrylic acid or the grafting being formed by it or comb-shaped polymer, as No. CAS be 1000934-04-1 can Tersperse

the copolymer that 2500 (Huntsman) are commercial or be 119724-54-8 No. CAS can Atlox

4913 (Uniqema) commercial copolymer.

In particularly preferred embodiment of the present invention, this emulsion comprises at least one non-ionic polymer surfactant with at least one polyether group, especially c.24 the non-ionic polymer surfactant of group or c.25, and at least one other surfactant, the latter is selected from non-polymer non-ionic surface active agent, anion non-polymer surfactant and anionic polymer surfactant.Preferably other surfactants be selected from c.6, group c.7, c.8, c.9, c.12, c.14 and c.15.In particularly preferred embodiment of the present invention, this emulsion comprises at least one non-ionic polymer surfactant, especially c.24 the non-ionic polymer surfactant of group or c.25, and at least one other surfactant, the latter is selected from anionic polymer surfactant, especially c.12 group.In another particularly preferred embodiment of the present invention, this emulsion comprises at least one non-ionic polymer surfactant, especially c.24 the non-ionic polymer surfactant of group or c.25, and at least one other surfactant, the latter is selected from anion non-polymer surfactant, especially c.6, c.7 or c.9 group.

The emulsion providing in a) in the inventive method step can be prepared by preparing any conventional method of the aqueous emulsion of agricultural chemical compound.

Preferably at first step a1) in therein this organic agricultural chemicals compound keep molten melt drop form, keep providing this emulsion at the temperature of the drop form that this agricultural chemical compound exists with molten condition.

If the temperature that wherein this organic agricultural chemicals compound keeps molten melt drop form conventionally fusing point-this agricultural chemical compound of this agricultural chemical compound can take the different polymorphics with different melting points exist as minimum fusing point-on, but also can be lower than its fusing point, yet preferably than the low 20K that is no less than of (minimum) fusing point, especially be no less than 10K, to avoid not controlled solidify/crystallization.Conventionally also tolerate the temperature slightly lower than fusing point, because when emulsification under surfactant exists, do not exist the crystallization agricultural chemical compound slow and melting under kind of crystalline substance may present melting point depression.This emulsion temperature that preferably wherein this organic agricultural chemicals compound keeps molten melt drop form with respect to (minimum) fusing point of this agricultural chemical compound be-20K is to+50K, especially-10K extremely+40K.The in the situation that of pyraclostrobin, wherein the emulsion droplet of pyraclostrobin keeps the temperature of molten condition to be generally 45-90 ℃, especially 50-80 ℃.

Then at second step a2) in this emulsion is cooled to significantly to the temperature lower than (minimum) fusing point of the crystalline form of this agricultural chemical compound.This temperature is conventionally than the low at least 5K of (minimum) fusing point of this agricultural chemical compound or 10K at least, preferably at least 15K, especially at least 20K, for example 10-60K, preferably 15-50K, especially 20-40K.The in the situation that of pyraclostrobin, this emulsion is preferably cooled to 5-50 ℃, preferably the temperature of 10-45 ℃, especially 15-40 ℃ or 15-35 ℃.

Preferably by the agricultural chemical compound of emulsification melting in the water containing one or more surfactants, prepare the emulsion of this agricultural chemical compound.Preferably this water contains one or more above-mentioned surfactants with above-mentioned concentration.As mentioned above, select wherein in water the temperature of the agricultural chemical compound of emulsification melting so that the organic agricultural chemicals compound of emulsification keeps the drop form of melting.Therefore, can be by this water preheat to temperature required or melt is heated to and reaches temperature required temperature when mixing.Certainly solid pesticide compound can also be suspended in water, this water may contain at least one or kinds of surface activating agent and optional other additive preparations, and this suspension is heated to the temperature more than melt temperature of described agricultural chemical compound.

When this melt of emulsification, conventionally agricultural chemicals drop is pulverized to realize required drop size.Average droplet size, the volume mean diameter of drop is preferably 0.5-10 μ m, and 1-5 μ m especially, by Dynamic Light Scattering Determination.

Pulverize preferably and realize by applying to shear in the emulsion process of melt.The device that is applicable to applying shearing comprises the device (such as referring to " Formulation Technology " Wiley-VCH 2001, the 136-144 pages such as H.Mollet) of any applicable wet-milling.Example comprises that height is cut and mixer, as Ultra-Turrax equipment, and dissolvers, static mixer, for example, have the system of mixing nozzle, ball mill, vibromill, agitation beads grinding machine, emulsification centrifuge, colloid mill, Cone crusher, circulation mill (agitating ball mill with pin grinding system), disc type grinding machine, doughnut grinding machine, bipyramid mill, mouthful sprocket dispersion machine or homogenizer and other homogenizers.Shearing can also mix by turbulent flow, fluid is injected to another fluid, vibration and cave mixture (for example using ultrasonic) applies.Pulverize at the temperature that this organic agricultural chemicals compound therein keeps molten melt drop form and carry out.At (minimum) fusing point with respect to this agricultural chemical compound, be preferably-20K is to+50K, and especially-10K pulverizes to the temperature of+40K.The in the situation that of pyraclostrobin, pulverize at 45-90 ℃, especially at the temperature of 50-80 ℃, carry out.

To the aqueous suspension that adds this agricultural chemical compound in the aqueous emulsion so obtaining.Reinforced preferably at the low at least 5K of (minimum) fusing point than this agricultural chemical compound, be usually 10K at least, preferred 15K at least, 20K at least particularly, for example, than the low 10-60K of (minimum) fusing point of agricultural chemical compound, preferably at the temperature of 15-50K, especially 20-40K, carry out.The in the situation that of pyraclostrobin, reinforced preferably at 5-50 ℃, preferably at the temperature of 10-45 ℃, especially 15-40 ℃ or 15-35 ℃, carry out.

Preferably select to add the suspension liquid measure in the aqueous emulsion of this agricultural chemical compound, so that the amount of contained this organic agricultural chemicals compound is 0.01-0.3 weight portion in this aqueous suspension, contained this agricultural chemical compound in 0.05-0.2 weight portion/1 weight parts water emulsion especially.Reinforced preferably by this aqueous emulsion is mixed and carried out with this aqueous suspension.Mix conventionally by using suitable mixing arrangement to carry out.The type of mixing arrangement is not too important, because crystallization is carried out fast.Suitable mixing arrangement comprises the volumetric standard that contains one or more agitators.Can also in one of above-mentioned reducing mechanism of having mentioned with regard to emulsification, feed in raw material/mix.What possibility was favourable but unnecessary is in aqueous suspension is added to this emulsion, to continue afterwards to pulverize, until reach desired particle size.Yet in the methods of the invention, crystalline rate completes conventionally very soon and conventionally within several seconds or several minutes.Therefore after, in aqueous suspension is added to this emulsion, conventionally do not need further pulverizing.

In aqueous suspension in adding the aqueous emulsion of this agricultural chemical compound, this agricultural chemical compound exists with basic crystalline form.In a preferred embodiment of the invention, this agricultural chemical compound being contained in aqueous emulsion is pyraclostrobin and is contained in the crystallization polymorphic that the agricultural chemicals in aqueous suspension is pyraclostrobin, especially the pyraclostrobin amount based on existing in this suspension is basic, and at least 90 % by weight are the crystalline form of the form IV as mentioned above or as described in WO 2006/136357.

Concentration in the aqueous suspension of this organic agricultural chemicals compound in adding this emulsion is generally 1-60 % by weight, particularly 5-50 % by weight, especially 10-40 % by weight.

Have been found that advantageously at step b) in add the volume average particle sizes of the crystalline pesticide compound existing in the aqueous suspension in this emulsion, the volume mean diameter that adds the crystalline pesticide compound particle in the aqueous suspension in this emulsion is 0.2-10 μ m, particularly 0.5-8 μ m, especially 1-5 μ m.

Add the aqueous suspension in the aqueous emulsion of this agricultural chemical compound can contain one or more surfactants and can further contain other additive preparations.The surfactant being contained in this aqueous suspension can be identical or different with the surfactant being contained in this aqueous emulsion.Preferably being contained in surfactant in this suspension is similar to and is contained in those in this emulsion.Preferred surfactant and surfactant combination are as preferred surfactant and surfactant, to combine those that mention with regard to aqueous emulsion.The gross weight of the concentration of surfactant in aqueous suspension based on aqueous suspension is generally 0.1-20 % by weight, preferably 0.5-15 % by weight, especially 1-10 % by weight.The weight ratio of agricultural chemicals and surfactant is generally 2: 1-50: 1, particularly 3: 1-20: 1.

The crystalline pesticide compound being contained in the aqueous suspension in the aqueous emulsion that adds this agricultural chemical compound is certainly identical with the agricultural chemical compound being contained in this aqueous emulsion.Yet this aqueous suspension can additionally contain one or more other agricultural chemical compounds.These other agricultural chemical compounds can be water miscible or as described below have limited water-soluble.Preferably be contained at least 20 % by weight, especially at least 40 % by weight that the crystalline pesticide compound identical with being contained in agricultural chemical compound in this emulsion in this suspension accounts for the agricultural chemical compound total amount being contained in this suspension.

In a preferred embodiment of the invention, in this aqueous emulsion, contained agricultural chemical compound is the crystallization polymorphic that in pyraclostrobin and this aqueous suspension in adding this emulsion, contained agricultural chemicals is pyraclostrobin, especially the pyraclostrobin amount based on existing in this suspension is basic, and at least 90 % by weight are the crystalline form of the form IV as mentioned above or as described in WO 2006/136357.

Add the aqueous suspension in the aqueous emulsion of this agricultural chemical compound to prepare by preparing the standardization program of the aqueous suspension of organic agricultural chemical compound.This aqueous suspension conventionally by the solid pesticide compound of basic crystallization is suspended in may contain one or more surfactants with stablize in the water of this agricultural chemical compound particle and subsequently agricultural chemical compound to the desired particle size of comminuted suspension prepare.Pulverizing can be similar to be carried out the described program of the pulverizing of emulsion droplet.

The special benefit of the inventive method is only in the initial period of the method, to require independent preparation will add the aqueous suspension in this aqueous emulsion.Once aqueous suspension be added to the aqueous suspension that just forms this agricultural chemical compound in the aqueous emulsion of this agricultural chemical compound, wherein this agricultural chemical compound particle is crystallization substantially.The granularity of this agricultural chemical compound particle be generally to this aqueous emulsion to scope.Therefore the suspension, so obtaining (or its part) can be as adding the suspension in this aqueous emulsion in another of the inventive method taken turns.Therefore can be used as simple batch processes and carry out the inventive method, can also be simply by getting aqueous suspension that a part forms in aqueous suspension is added to aqueous emulsion time and this part being recycled to the step b of claimed method) in and as semicontinuous method or continuation method, carry out the inventive method.This part is generally 0.01-0.3 weight portion, and especially 0.05-0.2 weight portion/1 weight portion is at step b) in the aqueous suspension that forms.Therefore, the inventive method has almost completely been avoided the effort preparation of solid crystal agricultural chemical compound material and has been processed.

As mentioned above, the step b of the inventive method) obtain the aqueous suspension of this agricultural chemical compound, wherein this agricultural chemical compound particle is crystallization substantially.The granularity of this agricultural chemical compound particle, the volume mean diameter of crystalline pesticide compound particle is generally 0.5-10 μ m, particularly 0.8-8 μ m, and 1-5 μ m especially, by Dynamic Light Scattering Determination.

This organic agricultural chemicals compound is at step b) in concentration in the gained aqueous suspension gross weight based on this aqueous suspension be generally 1-60 % by weight, particularly 5-50 % by weight, especially 10-40 % by weight.

At step b) in the aqueous suspension that obtains conventionally contain one or more be contained in aqueous emulsion in and added the surfactant in the aqueous suspension of the agricultural chemical compound in this aqueous emulsion.Step b in the method) gross weight of the aqueous suspension obtaining in based on this suspension be conventionally with 0.1-20 % by weight, preferred 0.5-15 % by weight, and especially the amount of 1-10 % by weight contains at least one surfactant.The weight ratio of agricultural chemicals and surfactant is generally 2: 1-50: 1, particularly 3: 1-20: 1.Have been found that to the stability of gained suspension advantageously surfactant be selected from those surfactants and the surfactant combination that in the aqueous emulsion with regard to this agricultural chemical compound, contained surfactant is mentioned as preferred or particularly preferred surfactant.

As mentioned above, at the inventive method step b) in the aqueous suspension that obtains can be directly as the aqueous suspension concentrate preparaton of this agricultural chemical compound.Yet, at the inventive method step b) in the aqueous suspension that obtains stable preparaton, the especially matrix of aqueous suspension concentrate that can also optionally contain described organic agricultural chemicals compound as preparation together with one or more other additive preparations and/or one or more other organic or inorganic agricultural chemical compounds.

Term used herein " aqueous suspension concentrate " comprises any pesticide preparation agent, and wherein this agricultural chemical compound exists with the particle form being suspended in water.Water can be that water or the cumulative volume based on water contain the mixture of the water of 20 volume % water miscibility solvent antifreezing agent as described herein at the most.Water can also contain one or more surfactants of being dissolved in wherein and/or the water soluble pesticide compound of one or more dissolvings, and they are not considered in water.Particularly, term used herein " aqueous suspension concentrate " comprises the aqueous suspension concentrate of land for growing field crops application, and it is also referred to as SC preparaton, and the aqueous suspension concentrate preparaton of seed treatment, and it is also referred to as FS preparaton.

One or more other additive preparations can be added in step b simply) in the aqueous suspension that obtains, preferably use mixing arrangement if agitator or static mixer are to realize additive preparation being uniformly distributed in final preparaton.Additive preparation can directly or with aqueous suspension or aqueous solution form add.

Can add in principle any normal compound additive.Normal compound additive may depend in a known way active component and for example comprise that antifreezing agent, viscosity improver (thickener or rheology modifiers), defoamer (also referred to as antifoaming agent or foam inhibitor), bactericide, colouring agent are as dyestuff or pigment and adhesive.Such additive can be at the step b that carries out preparation method described herein) before or after mix in aqueous suspension concentrate.Preferably major part or all these additives are at the step b that carries out preparation method described herein) add afterwards.The additive capacity that is different from antifreezing agent is no more than 10 % by weight of said composition gross weight, especially 5 % by weight conventionally.

Suitable antifreezing agent comprises monohydric alcohol and polyalcohol, especially C ₁-C ₄alkanol and polynary C ₂-C ₄alcohol.C ₁-C ₄the example of alkanol for example comprises methyl alcohol, ethanol, normal propyl alcohol and isopropyl alcohol.Polynary C ₂-C ₄the example of alcohol comprises ethylene glycol, 1,2-PD, 1,3-PD, glycerine and BDO.Preferred antifreezing agent is selected from polynary C ₂-C ₄alcohol, more preferably ethylene glycol and 1,3-PD.The gross weight of the concentration of antifreezing agent in final suspending concentrate based on final suspending concentrate is no more than 20 % by weight conventionally, and the gross weight that is preferably based on final suspending concentrate is 0.1-20 % by weight, particularly 0.5-10 % by weight, especially 1-5 % by weight.

Suitable thickener is to affect the flow behavior of suspending concentrate and contribute to stablize this suspending concentrate with the compound of anti-caking.Thus, for example, can mention the commercially available thickener based on polysaccharide, as methylcellulose, carboxymethyl cellulose, hydroxypropyl cellulose (Klucel

grade), xanthans is (for example, with grade Kelzan

commercial or with Rhodopol by Kelco grade is commercial by Rhodia), synthetic polymer is as acrylate copolymer (Carbopol

grade), polyvinyl alcohol is (for example, from the Mowiol of Kuraray

and Poval

grade) or polyvinylpyrrolidone, silicic acid or phyllosilicate be as montmorillonite, attapulgite and bentonite, they can hydrophobization (with Attaclay

grade and Attaflow

grade is commercial by BASF SE; Or with Veegum grade and Van Gel grade is commercial by R.T.Vanderbilt).Xanthans and phyllosilicate and especially its mixture are preferred thickeners.The gross weight that the gross weight of the concentration of thickener in final suspending concentrate based on final suspending concentrate is conventionally no more than 2 % by weight and is preferably based on final suspending concentrate is 0.01-2 % by weight, particularly 0.02-1.5 % by weight, especially 0.1-1 % by weight.

Defoamer can be added in this suspending concentrate.The example of suitable defoamer for example comprises that polysiloxane emulsion is (as Drewplus grade, Silikon

sRE, the Rhodorsil of Wacker or Rhodia

), long-chain alcohol, fatty acid, organofluorine compound and composition thereof.

Can add bactericide to prevent microbiological attack with stable suspersion concentrate.Suitable bactericide for example based on isothiazolinone as with trade mark Mergal

k10, Proxel grade is by Avecia (or Arch) or Acticide

grade is as Acticide

mBS or Acticide

rS is by Thor Chemie and Kathon

grade is as Kathon the compound that MK is sold by Rohm & Haas.

The present composition can also optionally comprise colouring agent as pigment or dyestuff, if especially said composition will be for seed treatment object.The pigment or the dyestuff that are applicable to seed treatment preparaton are pigment blue 15s: 4, and pigment blue 15: 3, pigment blue 15: 2, pigment blue 15: 1, alizarol saphirol 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 4 8:2, pigment red 4 8:1, paratonere 57:1, paratonere 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment Green 7, Pigment white 6, pigment brown 25, alkaline purple 10, alkalescence purple 49, CI 45430, acid red 52, azogeramine 4, acid blue 9, acid yellow 23, alkali red 1:1 0, alkali red 1:1 08.

In addition, aqueous suspension obtained by the method for the present invention can be used conventional adhesive, aqueous polymer dispersion for example, water-soluble resin, for example water soluble alkyd resin, or wax (if especially will by said composition for seed treatment object) preparation.

In addition, aqueous suspension obtained by the method for the present invention can be prepared together with other agricultural chemical compounds.The character of other agricultural chemical compounds depends on naturally at step b) in contained agricultural chemical compound in gained aqueous suspension.Equally, the concentration of other agricultural chemical compounds and at step b) in gained aqueous suspension the weight ratio of contained the first agricultural chemical compound and other agricultural chemical compounds depend in a known way the type of the first and second agricultural chemical compounds.

This agricultural chemical compound can be any organic or inorganic agricultural chemical compound, and it is suitable as at step b) in the common agricultural chemicals of contained agricultural chemical compound in gained aqueous suspension.These other agricultural chemical compounds can be water miscible or can as described hereinly have limited water-soluble, preferred the latter.

Other agricultural chemical compounds can be used as solid material, for example, as powder, add.The further pulverising step of the mixture that now, gained mixture so obtains conventionally.Pulverize preferably and realize by the mixture of aqueous suspension and other agricultural chemical compounds is applied to shear.The device that is applicable to applying shearing comprises above-mentioned any high-shear device, and high shear mixer for example, as Ultra-Turrax equipment, and dissolvers, static mixer, for example, have the system of mixing nozzle, ball mill, vibromill, agitation beads grinding machine, colloid mill, Cone crusher, circulation mill (agitating ball mill with pin grinding system), disc type grinding machine, doughnut grinding machine, bipyramid mill, mouthful sprocket dispersion machine or homogenizer and other homogenizers.Pulverize therein first and any other organic agricultural chemicals compound keep carrying out at the temperature of solid particulate form.Preferably at the temperature of the low at least 10K of (minimum) fusing point than existing any agricultural chemical compound, pulverize.

Other agricultural chemical compounds also can be used as liquid, for example, as the aqueous solution or aqueous suspension, add.Now, needn't but likely make gained mixture carry out further pulverising step.The liquid that contains at least one other agricultural chemical compound reinforced conventionally by using mixing arrangement to carry out as agitator or static mixer, to realize fluid composition being uniformly distributed in final preparaton of containing at least one other agricultural chemical compound.The liquid that contains other agricultural chemical compounds can contain one or more surfactants and/or additive preparation.

Other additive preparations also can add in the reinforced process of other agricultural chemical compounds or after reinforced.

The gross weight of the total concentration of any organic agricultural chemicals compound in aqueous suspension concentrate preparaton based on this aqueous suspension is generally 1-60 % by weight, especially 5-55 % by weight, especially 10-50 % by weight.The relative quantity of first (crystallization) agricultural chemical compound and at least one other agricultural chemical compound is generally 20: 1-1: 20, especially 10: 1-1: 10 (weight ratios).

The preparaton so obtaining is aqueous suspension form (being aqueous suspension concentrate form), its first agricultural chemical compound that contains the suspended particulate form that is basic crystallization and at least one other agricultural chemical compound, the latter can exist with solid particulate form or dissolved form, and this depends on the solvability of at least one other agricultural chemical compound in water.The granularity of this agricultural chemical compound particle, the volume mean diameter of any solid chemical compound particle is generally 0.5-10 μ m, particularly 0.8-8 μ m, and 1-5 μ m especially, by Dynamic Light Scattering Determination.

As mentioned above, other agricultural chemical compounds can be selected from known applicable any agricultural chemical compound of preparing altogether with the first agricultural chemical compound.These other agricultural chemical compounds are selected from organic agricultural chemicals compound conventionally, especially organic fungicide compound, organic insecticide compounds and organic herbicide compound.

Other agricultural chemicals that are applicable to the object of the invention include but not limited to:

Organic fungicide, especially

Azole fungicide, as encircle penta azoles bacterium, oxole bacterium (epoxiconazol), triticonazole (triticonazol), Fluquinconazole (fluquinconazol), prothioconazoles (prothioconazol),

ether azoles (difenoconazol) or cyproconazole (cyproconazol), amide-type fungicide, as carboxin (carboxin), oxycarboxin (oxycarboxin), cyazofamid (cyazofamid), Boscalid (boscalid), isopyrazam, bixafen, penflufen, pyrrole metsulfovax (penthiopyrad), sedaxane, isotianil (isothianil), N-(3 ', 4 ', 5 '-trifluoro-biphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide (common name: fluxapyroxad), N-(4 '-trifluoromethylthio biphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide or other fungicide, as Delan (dithianon), pyrimethanil (pyrimethanil), Carbatene (metiram), mancozeb (mancozeb), captan (captan), folpet (folpet), tpn (chlorothalonil) or thiophanate methyl (thiophanat-methyl),

Insecticide, especially Phenylpyrazole insecticides, as Frontline (fipronil) or chlorantraniliprole (chlorantraniliprole), synthetic pyrethroid insecticide, as nail body cypermethrin (α-cypermethtrin), anabasine, as clothianidin (clothianidin), Diacloden (thiamethoxam) or Imidacloprid (imidacloprid), other insecticides are as Olivomitecidin (abamectin), Teflubenzuron (teflubenzuron) or metaflumizone (metaflumizone), weed killer herbicide is as glyphosate (glyphosate), grass ammonium phosphine (glufosinate), imazamox (imazomox), Arsenal (imazapyr), imazapic (imazapic), Imazethapyr (imazethapyr) or dicamba (dicamba), and

Growth inhibitor or growth retardant are as helped strong plain cation (mepiquat) or chlormequat (chlormequat);

And the salt of possible above-claimed cpd.

If pyraclostrobin is the first agricultural chemical compound, the suitable agricultural chemical compound that can prepare altogether with pyraclostrobin for example comprises:

Organic fungicide, especially

Azole fungicide, as encircle penta azoles bacterium, oxole bacterium, triticonazole, Fluquinconazole, prothioconazoles,

ether azoles or cyproconazole;

Amide-type fungicide, as carboxin, oxycarboxin, cyazofamid, Boscalid, isopyrazam, bixafen, penflufen, pyrrole metsulfovax, sedaxane, isotianil, N-(3 ', 4 ', 5 '-trifluoro-biphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N-(4 '-trifluoromethylthio biphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide or other fungicide, as Delan, pyrimethanil, Carbatene, mancozeb, captan, folpet, tpn or thiophanate methyl, insecticide, especially Phenylpyrazole insecticides, as Frontline or chlorantraniliprole, synthetic pyrethroid insecticide, as nail body cypermethrin, anabasine, as clothianidin, Diacloden or Imidacloprid, other insecticides are as Olivomitecidin, Teflubenzuron or metaflumizone,

Weed killer herbicide, as glyphosate, careless ammonium phosphine, imazamox, Arsenal, imazapic, Imazethapyr or dicamba, and

Growth inhibitor or growth retardant are as helped strong plain cation or chlormequat;

And the salt of possible above-claimed cpd.

In a preferred embodiment of the invention, the first agricultural chemical compound is that pyraclostrobin and other agricultural chemical compounds are selected from above-mentioned amide-type fungicide, especially penflufen, sedaxane, pyrrole metsulfovax, fluxapyroxad and N-(4 '-trifluoromethylthio biphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide.

In another preferred embodiment of the present invention, the first agricultural chemical compound is that pyraclostrobin and other agricultural chemical compounds are selected from above-mentioned health azole (conazole) fungicide, especially encircle penta azoles bacterium (methconazol), the mixture of oxole bacterium and oxole bacterium and Frontline.

In particular embodiment of the present invention, the first agricultural chemical compound is that pyraclostrobin and other agricultural chemical compounds are ring penta azoles bacterium.In another particular embodiment of the present invention, the first agricultural chemical compound is that pyraclostrobin and other agricultural chemical compounds are oxole bacterium.In another particular embodiment of the present invention, the first agricultural chemical compound is that pyraclostrobin and other agricultural chemical compounds are Boscalid.In another particular embodiment of the present invention, the first agricultural chemical compound is that pyraclostrobin and other agricultural chemical compounds are fluxapyroxad.In another particular embodiment of the present invention, the first agricultural chemical compound is that pyraclostrobin and other agricultural chemical compounds are the mixture of Frontline (fipronail) and oxole bacterium.In another particular embodiment of the present invention, the first agricultural chemical compound is that pyraclostrobin and other agricultural chemical compounds are Delan.In another particular embodiment of the present invention, the first agricultural chemical compound is that pyraclostrobin and other agricultural chemical compounds are tpn.

Aqueous suspension concentrate obtained by the method for the present invention is preparaton stable on physics and chemistry, its can be at the temperature of environmental temperature or rising or the temperature of variation stored for several weeks or several months or several years and do not form roughage or the caking of significant quantity even.Suspending concentrate is that dilution is stable, and even, after long term storage,, when dilute with water, they do not demonstrate remarkable separation or the layering of active component.Not bound by theory, the stability that it is believed that aqueous suspension concentrate obtained by the method for the present invention can ascribe the more regular form of crystalline pesticide compound particle to, and the agricultural chemical compound particle in the aqueous suspension concentrate obtaining with the standardization program of pulverizing crystalline material by comprising is contrary.

Aqueous suspension concentrate obtained by the method for the present invention can be used any large Tanaka of other preparatons of corresponding agricultural chemical compound to obtain therein.For example, if contained agricultural chemical compound is pyraclostrobin in aqueous suspension concentrate, this suspending concentrate can be for various cultivated plants, if wheat, rye, barley, triticale, oat, rice, corn, dogstail, banana, cotton, soybean, coffee, sugarcane, grape vine, fruit and ornamental plants and vegetables are as prevented and treated a large amount of harmful fungoids on cucumber, Kidney bean, tomato, potato and cucurbit and on the seed of these plants.Certainly aqueous suspension concentrate obtained by the method for the present invention can be used as the mixed thing pairing of the bucket with other preparatons.If for example in aqueous suspension concentrate, contained agricultural chemical compound is pyraclostrobin, this suspending concentrate can be used together from different agricultural chemical compound preparatons or one or more above-mentioned other agricultural chemicals of mentioning in WO 2006/136357 in a large number.

The following example further illustrates the present invention.

material

Poly-(ethylene glycol/propylene glycol block copolymer) butyl ether (Atlox of Uniqema that surfactant 1:HLB value is 17

g5000).

Surfactant 2: the sodium salt (Morwet of naphthaldehyde condensation compound

d425, Akzo Nobel)

Surfactant 3: the comb-shaped polymer of methyl methacrylate, methacrylic acid and (methoxy poly (ethylene glycol)) methacrylate, 33% solution in 1: 1 mixture of propylene glycol/water (for example can be used as Atlox 4913 is commercial by Uniqema).

Surfactant 4: poly-(ethylene glycol/propylene glycol/polyethyleneglycol block copolymer) (Pluronic PE 10500)

Surfactant 5: the sodium salt of phenolsulfonic acid/urea/formaldehyde condensation products (Wettol D1, BASF SE)

Surfactant 6: the ammonium salt of the Hemisulphate of ethoxylation triphenyl vinyl phenol (Soprophor 4D384)

Thickener 1: xanthans, Kelzan

s (Kelco).

Thickener 2: Liquid Green palygorskite suspension (21 % by weight: the Attaflow of BASF SE

fL).

Thickener 3: the 1 % by weight aqueous solution (Rhodopol of xanthans in the water that contains 2 % by weight propane diols and 0.5 % by weight bactericide 23)

Defoamer: Drewplus l768 (Ashland)

analyze:

Use Malvern Mastersizer 2000 by laser light scattering, under suitable dilution factor, to measure the granularity of aqueous emulsion and aqueous suspension.Size distribution is by being used the scattering pattern of Fraunhofer model analysis sample to calculate.

In the reflection geometric ranges of °-35 °, 2 θ=4, at 25 ℃, use Cu-K alpha ray to obtain X-ray powder diffraction figure with the increment of 0.02 ° active component being used afterwards by this suspension lyolysis preparation (deformulation) from the D-5000 diffractometer of Siemens.The 2 θ values that record are for calculating described interplanar distance d.

Use is measured fusing point and melting heat from the Simultaneous Thermal Analyzer STA 449 C Jupiter of NETZSCH in the scope of-5 ℃ to+80 ℃ by DSC, the rate of heat addition is 5K/min.Sample size is 5-10mg.To melting peak integration, provide the melting heat (joule/gram) of sample and the flex point that sample starts melting, be called melting initial.

Use is equipped with the crystallinity that the conventional polarizing microscope of hot platform is observed this agricultural chemical compound material.

Active component is used L-Column ODS by reversed-phase HPLC

post (150 * 4.6mm, df=5 micron) is accurate and peak area ratio mensuration with interior calibration.Use the volume injected of wavelength separated approximately 2 μ L under the column temperature of 55 ℃ of about 280nm.The mobile gradient for being formed by acetonitrile, methyl tertiary butyl ether(MTBE), water, isopropyl alcohol, methyl alcohol and phosphoric acid mutually.

syneresis:

When aging, suspending concentrate may be separated, thereby at top, produces the hyaline layer of continuous phase, and its emulsus layer by disperse phase supports.This process is called syneresis: the liquid continuous phase when storing in suspending concentrate is extruded.Parting material (%) is the tolerance of syneresis (%).This be the volume of syneresis liquid (clear liquid at top) divided by gross sample volume, be expressed as percentage.Syneresis value be 10% or less sample be considered to qualified.Syneresis value is less than 1% sample and demonstrates minimum separation, and is considered to excellent.

the preliminary test of crystallization inhibitory activity constituents mixt

At the temperature of 70 ℃ on microslide the conventional suspending concentrate of melting pyraclostrobin (for example, referring to following reference example 1) get back to 25 ℃.This produces the film of solid amorphous pyraclostrobin.The kind crystalline substance of crystal formation I and form IV is sprayed on this unformed layer and with the interval of 15 minutes and observes crystal.Can see that crystal growth surpasses the time of 4 hours, the crystal in growth has the shape of primary vaccination crystalline substance.This shows that final crystal structure (for pyraclostrobin) is definite by kind of crystal class type.

preparation procedure:

According to standard wet milling process, prepare suspending concentrate (reference example)

Reference example 1

3g surfactant 2 and 2g surfactant 1 are dissolved in 55g water, are then mixed to evenly.Then add 40g crystallization pyraclostrobin and use high shear mixer to disperse.Make 40% slurry by using Eiger Mini 50 ball mills that 0.8mm bead and bead load are 90%, until realize the granularity of approximately 2.0 μ m.

Reference example 2

10kg propane diols and 5kg surfactant 2 are dissolved in 40kg water, are then mixed to evenly.Then add 45kg crystallization pyraclostrobin and use high shear mixer to disperse.Make 45% slurry by using 5 liters of ball mills of Drais that 1.0mm bead and bead load are 70%, until realize the granularity of 2.0 μ m.

Reference example 3

7g ethylene glycol, 5g surfactant 2 and 3g surfactant 4 are dissolved in 55g water, are then mixed to evenly.Then add 30g crystallization pyraclostrobin and use high shear mixer to disperse.Make 30% slurry by using the Dynomill ball mill that 0.8mm bead and bead load are 80%, until realize the granularity of 2.0 μ m.

Reference example 4

1.1g surfactant 3 and 1.1g surfactant 1 are dissolved in 16.4g water, are then mixed to evenly.Then add the crystallization pyraclostrobin of 10.0g form IV and this slurry is used in Eiger medium mill the 1mm bead of 80% load grind, until realize the final size of 1 μ m.This produces the aqueous suspension that wherein pyraclostrobin exists with its form IV.

On more extensive, repeat the method and the suspension so obtaining is diluted to 21-25 % by weight activity component concentration with other additive preparations that add, obtain final suspending concentrate shown in table 2.

Reference example 5

1.1g surfactant 2 and 1.1g surfactant 1 are dissolved in 16.4g water, are then mixed to evenly.Then add the crystallization pyraclostrobin of 10.0g form IV and this slurry is used in Eiger medium mill the 1mm bead of 80% load grind, until realize the final size of 1 μ m.This produces the aqueous suspension that wherein pyraclostrobin exists with its form IV.

On more extensive, repeat the method and the suspension so obtaining is diluted to 21-25 % by weight activity component concentration with other additive preparations that add, obtain final suspending concentrate shown in table 2.Suspending concentrate prepared according to the methods of the invention

Embodiment 1:

6.3g surfactant 1 and 6.3g surfactant 3 are dissolved in 97.9g water, are then mixed to evenly.Then add 60.6g melting pyraclostrobin and this mixture pumping is passed through to colloid mill, until form the pyraclostrobin emulsion of approximately 3 μ m.Just after forming and in the microscopic examination of this emulsion being shown to this emulsion after 24 hours, contained pyraclostrobin is entirely unbodied and keeps amorphous at least 24 hours.

In this emulsion, add the aqueous suspension of 28.6g reference example 4 and mix in glass container.After 15 seconds, microscope detection sample shows complete crystallization.By dsc measurement, melting heat is measured the form IV that shows that this crystalline material is pyraclostrobin.The P-XRD that separates the pyraclostrobin of preparation confirms that this crystalline material is the form IV of pyraclostrobin substantially.

Embodiment 2:

In this emulsion, add the aqueous suspension of 28.6g reference example 4 and make this mixture continue to pass through colloid mill.After 15 seconds, microscope detection sample shows complete crystallization.By dsc measurement, melting heat is measured the form IV that shows that this crystalline material is pyraclostrobin.The P-XRD that separates the pyraclostrobin of preparation confirms that this crystalline material is the form IV of pyraclostrobin substantially.The suspension so obtaining is diluted to 21-25 % by weight activity component concentration with other additive preparations that add, obtains final suspending concentrate shown in table 2.

Embodiment 3:

By method described in embodiment 2, carry out embodiment 3, but there is following change.The suspension of use reference example 5 replaces the suspension of reference example 4 and surfactant 3 is replaced with to the surfactant 2 of same amount.The suspension so obtaining is diluted to 21-25 % by weight activity component concentration with other additive preparations that add, obtains final suspending concentrate shown in table 2.

Table 2:

Grind matrix	Reference example 4	Embodiment 2	Reference example 5	Embodiment 3
					Pyraclostrobin	21.0％	25.0％	21.0％	23.0％
Surfactant 1	3.8％	3.8％	3.8％	3.8％
					Surfactant 2	0.0％	0.0％	3.8％	3.8％

Grind matrix	Reference example 4	Embodiment 2	Reference example 5	Embodiment 3
					Surfactant 3	3.8％	3.8％	0.0％	0.0％
Propane diols	2.5％	2.5％	2.5％	2.5％
					Thickener 1	0.2％	0.2％	0.2％	0.2％
Thickener 2	0.4％	0.4％	0.4％	0.4％
					Defoamer	0.1％	0.1％	0.1％	0.1％
Water	To 100%	To 100%	To 100%	To 100%

All amounts provide with % by weight.

Preparaton is stored to 4 weeks respectively at 40 ℃ and 50 ℃.Melting heat, the melting of after this time, analyzing preparaton are initial, active component content and granularity compare with initial value.The results are shown in following table 3-6:

Table 3: according to the preparaton of reference example 4

	Initially	Within 4 weeks ,@is 40 ℃	4 weeks, 50 ℃
				AI content [%] ¹⁾	21.0	21.0	21.0
Melting initial [℃]	53.0	54.0	54.8
				Melting heat [J/g]	76.7	76.7	76.2
Syneresis [%]	0	～0.01	～0.01
				D ₅₀[μm]	1.70	2.10	2.89

1) concentration of active component, % by weight

Table 4: according to the preparaton of embodiment 2

	Initially	Within 4 weeks ,@is 40 ℃	4 weeks, 50 ℃
				AI content [%] ¹⁾	25.1	25.2	25.2
Melting initial [℃]	52.8	52.8	53.0
				Melting heat [J/g]	76.1	75.3	75.9
Syneresis [%]	0	0.01	～0.01
				D ₅₀[μm]	2.61	2.50	2.73

Table 5: according to the preparaton of reference example 5

	Initially	Within 4 weeks ,@is 40 ℃	4 weeks, 50 ℃
				AI content [%] ¹⁾	20.9	20.7	21.0
Melting initial [℃]	52.0	52.4	54.9
				Melting heat [J/g]	75.3	75.9	77.0
Syneresis [%]	0	10	10
				D ₅₀[μm]	1.41	1.75	2.54

Table 6: according to the preparaton of embodiment 3

	Initially	Within 4 weeks ,@is 40 ℃	Within 4 weeks ,@is 50 ℃
				AI content [%] ¹⁾	23.2	23.0	23.2
Melting initial [℃]	51.1	51.9	54.8
				Melting heat [J/g]	71.0	71.4	71.0
Syneresis [%]	0	10	10
				D ₅₀[μm]	1.66	2.19	2.64

The result being summarized in table 3-6 shows that preparaton obtained by the method for the present invention and the suspending concentrate of being prepared by conventional method have similar stability.

Embodiment 4: the aqueous suspension concentrate that preparation contains pyraclostrobin and ring penta azoles bacterium

(a) 2.2g surfactant 3 and 2.2g surfactant 1 are dissolved in 21.2g water, are then mixed to evenly.Then add the crystallization pyraclostrobin of 13.8g form IV and in ball mill, use the 1mm bead of 80% load to grind this slurry, until final size is 1.5 μ m (volume mean diameter).Use 100 mesh sieves to filter this suspension, to remove not ground material and cracked bead.Obtain thus 35 % by weight aqueous suspensions, wherein pyraclostrobin exists with its form IV.

(b) 19.6g surfactant 3 and 19.6g surfactant 1 are dissolved in 191g water, are then mixed to evenly.Add 0.4g defoamer and this mixture is heated to 65-75 ℃.In this solution, add 124g melting pyraclostrobin (70-85 ℃) and this mixture pumping is passed through to colloid mill, until form the pyraclostrobin emulsion that is less than 10 μ m.When continuing to make this mixture by colloid mill, this emulsion is cooled to 35-40 ℃.At 23-40 ℃, in this emulsion, add the aqueous suspension of 39.4g step (a) and make this mixture continue to pass through colloid mill 15 minutes.The suspension that uses 100 mesh sieves to filter so to obtain is to remove large material.

The microscope detection sample of this suspension shows complete crystallization.By dsc measurement, melting heat is measured the form IV that shows that this crystalline material is pyraclostrobin.The P-XRD that separates the pyraclostrobin of preparation confirms that this crystalline material is the form IV of pyraclostrobin substantially.The volume mean diameter that the suspension so obtaining contains 35 % by weight pyraclostrobins and pyraclostrobin particle is less than 2.3 μ m.

(c) 8.2g surfactant 3 and 8.2g surfactant 1 are dissolved in 80g water, are then mixed to evenly.Add 0.15g defoamer.Then under agitation adding 51.9g to encircle penta azoles bacterium and in ball mill, use the 1mm bead of 80% load to be ground to final size this slurry is 1.5 μ m (volume mean diameter).Use 100 mesh sieves to filter this suspension, to remove not ground material and cracked bead.This obtains the aqueous suspension of 35 % by weight ring penta azoles bacterium.

(d), by 15g liquid thickener 2,0.5g defoamer and 31g propane diols add in 217g water and are stirred to evenly.Then under agitation add 200g thickener 3 (1% solution).Then under agitation add that moisture pyraclostrobin suspension that 390g obtains in step (b) and 146.9g obtain in step (c) containing water ring penta azoles bacterium suspension and continue to stir until this mixture is even.The suspension that uses 100 mesh sieves to filter so to obtain is to remove large material.

Formulation thus obtainedly contain 13.6 % by weight pyraclostrobins and 5.1 % by weight ring penta azoles bacterium.The viscosity of this preparaton is 500-1000cps, uses 2# spindle to measure according to STM-35.0 at 20 ℃.The volume mean diameter of particle is less than 2 μ m.This preparaton keeps stablizing more than 3 months at 54 ℃, and granularity slightly increases.This preparaton keeps stablizing more than 3 months and is not stratified at-10 ℃.Embodiment 5: the aqueous suspension concentrate that preparation contains pyraclostrobin and oxole bacterium

(a) by 4.1g surfactant 4,2.8g surfactant 5 and 0.1g defoamer add in 41.4g water, are then mixed to evenly.Then add the crystallization pyraclostrobin of 37.2g form IV and in ball mill, use the 1mm bead of 80% load to grind this slurry, until final size is 1.5 μ m (volume mean diameter).Use 100 mesh sieves to filter this suspension, to remove not ground material and cracked bead.Obtain thus 40 % by weight aqueous suspensions, wherein pyraclostrobin exists with its form IV.

(b) by 23.5g surfactant 4,16.0g surfactant 5 and 1.1g defoamer add in 248g water, be then mixed to evenly and this mixture is heated to 65-70 ℃.In this solution, add 195.8g melting pyraclostrobin (70-85 ℃) and this mixture pumping is passed through to colloid mill, until form the pyraclostrobin emulsion that is less than 10 μ m.When continuing to make this mixture by colloid mill, this emulsion is cooled to 40 ℃.At 40 ℃, in this emulsion, add the aqueous suspension of 85.6g step (a) and make this mixture continue to pass through colloid mill 15 minutes.The suspension that uses 100 mesh sieves to filter so to obtain is to remove large material.The volume mean diameter that the suspension so obtaining contains 40 % by weight pyraclostrobins and pyraclostrobin particle is less than 2.3 μ m.

(c) in the moisture pyraclostrobin suspension under agitation obtaining in step (b) to 570.2g, add 144g oxole bacterium and 130.5g water and make this mixture pass through colloid mill 15 minutes at 25 ℃.Then make this mixture by using the ball mill twice of the 0.6-0.8mm bead of 80% load, until final size is 2 μ m (volume mean diameter).In this suspension, add 3.4g defoamer, 67.6g propane diols, 0.22g thickener, 0.18g bactericide (Acticide MBS) and 80.3g water are also stirred to this mixture evenly.

Formulation thus obtained 22.8 % by weight pyraclostrobins and the 14.4 % by weight oxole bacteriums of containing.The viscosity of this preparaton is 500-1000cps, uses 2# spindle to measure according to STM-35.0 at 20 ℃.The volume mean diameter of particle is less than 2 μ m.

Embodiment 6: the aqueous suspension concentrate that preparation contains pyraclostrobin and fluxapyroxad

Under agitation following ingredients is added in suitable container with following order:

This mixture is heated to 70 ℃.Then in high shear mixing (10000-15000rpm), add the pyraclostrobin (based on 100% purity) of 160.3g melting (approximately 75 ℃) under approximately 20 minutes.Then the emulsion of formation is cooled to 40 ℃, still continues high shear mixing simultaneously.When the temperature of this mixture reaches 40 ℃, use immediately the final preparaton that contains pyraclostrobin and fluxapyroxad and there is following total composition of about 116g (10 % by weight of total preparaton) previous round to this emulsion inoculation.A few minutes intercrystalline start and continue under high shear mixing cooling, until reach the temperature of 20 ℃.Crystallization is monitored by microscope.After 30 minutes, size distribution reaches D ₅₀< 2 μ m and D ₉₀< 20 μ m.Then add the former medicine fluxapyroxad of 299.7g (based on 100% purity) and continue and mix extra 30 minutes.

Then make this suspension by suitable ball mill, use the bead of 0.75-1mm diameter.When reaching described size distribution, complete grinding.

Finally under agitation add 2.5g to be dissolved in xanthans and the 4g propane diols in 20g water, until xanthans is dispersed.Then under agitation add 2g Acticide MBS and 5g Silicon SRE (defoamer).Continue to stir extra 5 minutes.

Formulation thus obtained have a following composition:

Final composition:

Embodiment 7: the aqueous suspension concentrate that preparation contains pyraclostrobin

(a) under agitation in the reaction vessel that contains 60g water, add 10.5g surfactant 3,3.7g surfactant 6,0.6g defoamer and 35.6g glycerine also stir this mixture until evenly.Then add the crystallization pyraclostrobin of 60g form IV and in ball mill, use the 1mm bead of 80% load to grind this slurry, until final size is 1.5 μ m (volume mean diameter).Use 100 mesh sieves to filter this suspension, to remove not ground material and cracked bead.Obtain thus 35 % by weight aqueous suspensions, wherein pyraclostrobin exists with its form IV.

(b) under agitation in the reaction vessel that contains 600g water, add 70g surfactant 3,24.6g surfactant 6 and 4g defoamer also stir this mixture until evenly.Then this mixture is heated to 65-70 ℃.In this solution, add 402g melting pyraclostrobin (70-85 ℃) and this mixture pumping is passed through to colloid mill, until form the pyraclostrobin emulsion that drop size is less than 10 μ m.When continuing to make this mixture by colloid mill, this emulsion is cooled to 40 ℃.At 40 ℃, in this emulsion, add the aqueous suspension of 110g step (a) and make this mixture continue to pass through colloid mill other 15 minutes.The suspension that uses 100 mesh sieves to filter so to obtain is to remove large material.The volume mean diameter that the suspension so obtaining contains 33 % by weight pyraclostrobins and pyraclostrobin particle is less than 2.3 μ m.This suspension keeps stablizing the several months and not alligatoring.

Claims

1. a method of preparing the aqueous suspension of organic agricultural chemical compound, water-soluble the be no more than 2g/l of described compound at 20 ℃ and fusing point are no more than 110 ℃ and can form at least one crystalline form, wherein said organic agricultural chemicals compound exists with the particle form of basic crystallization and is wherein present in the described agricultural chemical compound in described aqueous suspension at least 90% and is crystalline state, and described method comprises:

A) provide the aqueous emulsion of described organic agricultural chemicals compound, wherein said organic agricultural chemicals compound exists with the drop form of the amorphous form of described organic agricultural chemicals compound, wherein said amorphous form is that melt, mistake sloppy heat body or solid amorphous form and the concentration of wherein said organic agricultural chemicals compound in described aqueous emulsion are 10-50 % by weight, and

B) add the aqueous suspension of described organic agricultural chemicals compound, wherein said organic agricultural chemicals compound exists with the particle form of basic crystallization, and be wherein present in the described agricultural chemical compound in described aqueous suspension at least 90% and be crystalline state,

Step b wherein) at the temperature of feeding in raw material below the melt temperature of the crystalline form of described organic agricultural chemicals compound in, carry out and be wherein chosen in step b) in the relative quantity of the aqueous suspension that adds and described aqueous emulsion so that the described organic agricultural chemicals compound amount containing in described aqueous suspension is the agricultural chemical compound containing in aqueous emulsion described in the weight portion of 0.01-0.3 weight portion/1.

According to the process of claim 1 wherein that described organic agricultural chemicals compound is selected from that aldrin, alachlor, triazotion, benfluralin, bensultap, Citrazon, bifenthrin, binapacryl, bromophos, fenisobromolate, Amex820, chlorphoxim, chlopyrifos, fluchloralin, fluroxypyr, imines bacterium, lorox, metazachlor, ring penta azoles bacterium, afesin, isopropyl disappear, pendimethalin, phosmet, ZEN 90160, fluorine pyrrole acyl grass amine, pyraclostrobin, tefluthrin, oxime bacterium ester and proproanmide.

3. according to the method for claim 1 or 2, wherein said organic agricultural chemicals compound is pyraclostrobin.

4. according to the method for claim 3, wherein at step b) in add the aqueous suspension of pyraclostrobin, wherein pyraclostrobin exists with the form of its form IV substantially.

5. according to the method for claim 1 or 2, wherein said feeding in raw material carried out at the temperature of the low 10-60K of fusing point than the described crystalline form of described organic agricultural chemicals compound.

6. according to the method for claim 1 or 2, the volume averaging drop size of wherein said organic agricultural chemicals compound drop in described aqueous emulsion is 0.5-10 μ m.

7. according to the method for claim 1 or 2, wherein said organic agricultural chemicals compound is at step b) in concentration in the described aqueous suspension that adds be 1-60 % by weight.

8. according to the method for claim 1 or 2, wherein said organic agricultural chemicals compound particle is at step b) in volume average particle sizes in the described aqueous suspension that adds be 0.2-10 μ m.

9. according to the method for claim 1 or 2, wherein said aqueous emulsion additionally contains at least one anion with at least one polyether group or non-ionic polymer surfactant.

10. according to the method for claim 1 or 2, wherein said aqueous emulsion additionally contains at least one anionic polymer surfactant with polyether lateral chain.

11. according to the method for claim 9, and wherein said anionic polymer surfactant is the polymer having with the carbon skeleton of carboxylate groups and polyether lateral chain.

12. according to the method for claim 10, and wherein said aqueous emulsion additionally contains at least one non-ionic surface active agent with at least one polyether group.

13. according to the method for claim 1 or 2, and wherein step a) comprising:

A.1) at described organic agricultural chemicals compound, keep described agricultural chemical compound to be the aqueous emulsion that described organic agricultural chemicals compound is provided at the temperature of drop form of molten state, and

A.2) optionally the aqueous emulsion of described organic agricultural chemicals compound is cooled to than the temperature of the low at least 10K of the fusing point of the crystalline form of described organic agricultural chemicals compound.

14. according to the method for claim 13, and wherein step is a.1) comprise at the temperature that the melt of described organic agricultural chemicals compound is provided and is molten state in described organic agricultural chemicals compound maintenance the emulsification in water of described melt.

15. 1 kinds of methods of preparing aqueous pesticide preparaton with the aqueous suspension concentrate form that contains at least one organic agricultural chemicals compound, water-soluble the be no more than 2g/l of described compound at 20 ℃ and fusing point are no more than 110 ℃ and can form at least one crystalline form, described method comprises by prepare the aqueous suspension of described organic agricultural chemicals compound according to the method for any one in claim 1-14, wherein said organic agricultural chemicals compound exists with the particle form of basic crystallization and is wherein present in the described agricultural chemical compound in described aqueous suspension at least 90% and is crystalline state, described method further comprises at least one additive preparation is added in the aqueous suspension of described organic agricultural chemicals compound.

16. according to the method for claim 15, and wherein said additive preparation is selected from antifreezing agent, viscosity improver, defoamer, bactericide and colouring agent.

17. according to the method for claim 15 or 16, and it further comprises and adds at least one other organic agricultural chemicals compound.

18. according to the method for claim 17, the water-soluble 2g/l of being no more than that wherein said other organic agricultural chemicals compounds have at 20 ℃.

19. according to the method for claim 18, wherein said other organic agricultural chemicals compounds be selected from ring penta azoles bacterium, oxole bacterium, triticonazole, Fluquinconazole, prothioconazoles,

ether azoles, cyproconazole, carboxin, oxycarboxin, Boscalid, isopyrazam, bixafen, penflufen, pyrrole metsulfovax, sedaxane, isotianil, N-(3', 4', 5'-trifluoro-biphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N-(4'-trifluoromethylthio biphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, Delan, pyrimethanil, Carbatene, mancozeb, captan, folpet, tpn, thiophanate methyl, Frontline, Teflubenzuron, nail body cypermethrin, clothianidin, Diacloden, Imidacloprid, Olivomitecidin, chlorantraniliprole, metaflumizone, glyphosate, grass ammonium phosphine, imazamox, Arsenal, imazapic, Imazethapyr, dicamba, help strong plain cation and chlormequat and the salt of above-claimed cpd if possible.

20. according to the method for claim 18 or 19, and wherein said other organic agricultural chemicals compounds add with aqueous suspension form.